JPH0127103B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an injection moldable wholly aromatic copolyester resin composition which has good moldability and excellent various physical properties.

More specifically, the present invention combines glass fibers having an appropriate diameter and average length with a wholly aromatic copolyester mainly containing an oxybenzoyl compound, resulting in excellent moldability and mechanical and thermal resistance. The present invention relates to the production of a wholly aromatic copolyester resin composition with excellent physical properties.

Fully aromatic copolyesters have excellent properties based on their structure, but they stand out among all resins in terms of heat resistance. However, because it has heat resistance, it has the disadvantage of poor moldability. Copolymerization reaction is often used as a method to improve moldability, but in the case of oxybenzoyl compounds, for example, improvements can be made using copolyesters, as shown in Japanese Patent Publication No. 47-47870 and Japanese Patent Application Laid-open No. 50-43223. ing.

However, even in the case of these copolyesters, moldability and mechanical properties are still insufficient in many respects, and the high cost resulting from the cost of the copolymerization monomer is also a problem. To this end, as a result of intensive research into ways to improve moldability and mechanical properties by adding various fillers to the composition, we found that glass fibers with appropriate diameters and average lengths were made with a completely aromatic composition centered on oxybenzoyl compounds. Moldability in combination with group copolyester resins,
The present invention has been achieved to obtain a composition with excellent mechanical properties.

That is, the present invention is based on the general formula (In the formula, X is a hydrocarbon group having 1 to 10 carbon atoms, -O
-, -SO ₂ -, -SO-, -S-, -CO-, and m and n are 0 or 1. d≠0, and the oxybenzoic acid moiety has 50% or more of the para form.
When e, f≠0, e/f is a value from 0.90 to 1.10, and when e=f=0, the oxybenzoic acid moiety is a compound selected from at least two ortho, meta, and para forms. It is polymerization. ) with a diameter of 1 to 50 μm and an average length of 30
~1000μm glass fibers at 80% by weight of the entire composition
The following describes the wholly aromatic copolyester resin composition obtained by filling.

Components of the wholly aromatic copolyester resin used in the present invention include, for example, salicylic acid, meta, paraoxybenzoic acid, terephthalic acid, isophthalic acid,
Hydroquinone, resorcinol, 4,4'-diphenol, 4,4'-thiodiphenol, 4,4'-dioxydiphenyl sulfone, 4,4'-dioxydiphenyl sulfoxide, 4,4'-dioxybenzo Phenone, 4,4'-dioxydiphenyl ether, and derivatives thereof can be used. The method for polymerizing copolyester using these materials was published in 1973.
Suspension polymerization methods and bulk polymerization methods as shown in JP-A-47870, JP-A-50-43223, and JP-A-54-46291 are considered preferable, but are not particularly limited thereto.

As for the glass fiber used in the present invention, commercially available ones can be used in terms of composition, but alkali-free glass is preferable. It has excellent mechanical strength and is not easily affected by moisture, so it is suitable for use in reinforcing wholly aromatic copolyester resins. In terms of morphology, the chopped strands commonly used to strengthen thermoplastic resins have a diameter of 3 to 20 μm and are made up of several hundred fibers with a length of 1 to 10 mm. However, when this chopped strand is used as it is to strengthen a wholly aromatic copolyester resin, due to the physical properties of the resin such as low adhesion to metals, it cannot be used in an extruder or in a kneading device under normal processing conditions. As a result, the collected chopped strands are not unraveled and are extruded as they are without sufficient cutting, making it difficult to pelletize the resulting strands. Even if pelletization can be performed using a conventional method, a sufficient reinforcing effect cannot be obtained because the fibers are insufficiently dispersed.

Furthermore, when the sizing agent of the chopped strands is removed by heat treatment, chemical treatment, etc., the fibers become thread-like and bulky, making them extremely difficult to use in practice.

On the other hand, milled glass fibers, which are mainly used for reinforcing thermosetting resins, have a diameter of 3 to 3.
20μm, average length is less than 30μm, and the fibers are generally not bundled, but when using this milled fiber, it is possible to disperse it into the resin using a normal extruder or kneading device. However, the reinforcing effect is low. The same effect can be obtained using glass beads having an average particle size of 1 to 30 μm.

However, the diameter is 1 to 50 μm, preferably 3 to 50 μm.
When using glass fibers with a diameter of 20 μm and an average length of 30 to 1000 μm, preferably a morphology ratio of 3 to 100, which is the ratio of length to diameter, the workability during compounding is good and the fibers are uniformly dispersed. Thus, a wholly aromatic copolyester resin composition can be obtained which has a good molded appearance, a high reinforcing effect, and excellent performance.

There are no particular limitations on how to make glass fibers having the above-mentioned diameter, length, and form ratio;
Preferably, long fibers are cut and/or pulverized.

The amount of glass fiber filled into the resin is not particularly limited, but a range of 10 to 50% by weight is suitable for obtaining the highest reinforcing effect, but depending on the purpose.
It is possible to fill up to 80% by weight. Filling with more than 80% by weight is not practical because sufficient strength cannot be obtained.

Regarding the surface treatment of glass fibers, either no sizing agent is used, or even if there is, the surface treatment is used to the extent that the glass fibers can be dispersed to the extent that they can fully exhibit their properties when blended with the resin. is desirable, and commercially available coupling agents such as silane-based, chromium-based, phosphoric acid-based, etc. can be used as they are.

The wholly aromatic copolyester resin composition of the present invention may contain various other additives, such as stabilizers, flame retardants, modifiers, moldability improvers, crystallization promoters, fillers, and reinforcing materials other than glass fibers. It may be contained, and other thermoplastic resins or thermosetting resins may be contained within a range that does not impair the properties aimed at by the present invention.

The composition of the present invention can be manufactured by various methods. For example, a method in which glass fibers are allowed to coexist during polymerization of a wholly aromatic copolyester or post-treatment of a polymer, a method in which the resin and glass fibers are placed in an extruder or a kneading device, and a method in which predetermined glass fibers are The method described above or the method of treating the resin containing the resin together with the resin at the time of molding can be employed.

The present invention will be explained below with reference to Examples, but these Examples do not limit the scope of the present invention, but rather indicate preferred embodiments of the present invention. The diameter and average length of the glass fibers used in the examples were calculated by determining the distribution from microscopic photographs.

Example 1 430 parts of phenyl paraoxybenzoate, 203 parts of terephthalic acid chloride, and 2000 parts of diethylbenzene were placed in a polymerization tank having an anchor-shaped stirring blade and a small gap between the tank wall and the stirring blade, and the mixture was heated under a nitrogen atmosphere. And so. The system temperature was set to 180°C and refluxed at this temperature. Hydrogen chloride was generated as the temperature rose. This was neutralized with an aqueous caustic soda solution, and the amount of hydrogen chloride recovered was measured. Hydrogen chloride recovery rate is 90%
After reaching 150℃, let the reaction continue for another 30 minutes and increase the temperature to 150℃.
℃, 186 parts of 4,4'-dioxydiphenyl was added, thoroughly stirred, and the temperature was raised to 230°C under a nitrogen atmosphere while distilling diethylbenzene.

The temperature was raised from 230°C to 320°C over 10 hours, and the reaction was continued while removing the generated phenol.
The reaction was further carried out at 320°C for 10 hours. As time passed, an increase in torque was observed, but after 10 hours, a decrease in torque was observed. The temperature was gradually raised without increasing the torque, and polymerization was carried out at 340°C for 2 hours, followed by cooling. When the temperature reached 200°C, the powder polymer was taken out of the tank. The amount recovered was 523 parts, which was 94% of the theoretical amount. 500 parts of this polymer and diameter
333 parts of pulverized glass fiber with a diameter of 13 μm and an average length of 50 μm (form ratio ~4) was mixed (weight fraction of glass fiber in the composition: 40%), and the mixture was heated in a single-screw extruder manufactured by Tanabe Plastic Machinery VS-. 30-28 (screw diameter 30mm,
L/D~28) was used to granulate the mixture at a cylinder temperature of 340°C and a screw rotation speed of 50 rpm, and then injection molded at a cylinder temperature of 380°C using a Neomattu N47/28 injection molding machine manufactured by Sumitomo Heavy Industries.

The granulation property, injection moldability, and appearance of the molded product were good, and the tensile strength was 950 Kg/cm ² and the elongation at break was 4.5%, so that the product was satisfactory in terms of strength. Furthermore, the molding shrinkage rate was 3/1000, and the variation from shot to shot was small. The brightness of the molded product was measured with a Hunter color meter and was found to be 63.2.

Comparative Example 1 500 parts of a polymer made in the same manner as in Example 1 was mixed with a commercially available chopped strand CS-03-MA-
497 (manufactured by Asahi Fiberglass) 333 parts were mixed.
The fiber length of this glass fiber is approximately 3 mm. Granulation was attempted under the same conditions as in Examples, but the supply was unstable and the glass fibers remained bundled in the extruded strands, making cutting virtually impossible.

Comparative Example 2 The glass fiber used in Comparative Example 1 was preheated at 400°C for 50 minutes.
Heat treated for hours. Comparative example 1 using the same ratio of this treated product
An attempt was made to granulate the glass fibers by mixing them with the resin in the same manner as above, but since the glass fibers became thread-like and bulky, the supply was extremely unstable and good granulation could not be achieved.

Comparative Example 3 500 parts of a polymer made in the same manner as in Example 1 was mixed with commercially available milled fiber (manufactured by Nippon Glass Fiber Co., Ltd.).
EVS, diameter 9-13 μm, average length 10-20 μm) 333
The mixture was mixed, granulated under the same conditions as in Example 1, and injection molded. Workability during granulation and injection molding was good, but the strength of the molded product was low and the tensile strength was low.
The weight was 600 Kg/cm ² and the elongation at break was 3%, resulting in insufficient performance.

Example 2 In the same manner as in Example 1, diethylbenzene was replaced with xylene, and p-oxybenzoic acid and terephthalic acid chloride were reacted under reflux at 140°C for 5 hours. Collecting hydrogen chloride generated during the reaction
It was 93%. 4,4'-diacetoxydiphenyl was added to this, and the same treatment as in Example was carried out to polymerize. The yield of the obtained polymer was 534 parts, which was a yield of 96%. This has a diameter of 13μm and an average length of 80μm.
(form ratio ~6) of crushed glass fibers were mixed at a weight ratio of 30% in the composition. After granulation under the same conditions as in Example 1, injection molding was carried out at 380°C. There were no problems during granulation and molding, and a molded product with a good surface was obtained. The molded product had a tensile strength of 1200 Kg/cm ² and an elongation at break of 6.0%, which was satisfactory in terms of strength. The molding shrinkage rate was 3/1000, and the variation between shots was small. The brightness of the molded product was 65.8.

Comparative Example 4 330 parts of glass beads with an average particle size of 25 μm (manufactured by Toshiba Balloteini Corporation, 30μ spherical beads) were mixed with 500 parts of a polymer prepared in the same manner as in Example 2, and the mixture was treated under the same conditions as in Example 1. Mixed, granulated and injection molded at 380°C. Workability during granulation and molding was good, and the surface condition of the molded products was also good.
When a tensile test was conducted, the tensile strength was 620 Kg/cm ² and the elongation at break was 3.3%, indicating that insufficient performance was obtained.

Example 3 860 parts of phenyl paraoxybenzoate, 1600 parts of hydrogenated terphenyl, 572 parts of diphenyl terephthalate, 64 parts of diphenyl isophthalate, and 220 parts of hydroquinone were placed in the reaction tank used in Example 1.
The temperature was raised to 250℃ in about 2 hours under a nitrogen atmosphere.
The temperature is raised from 250°C to 320°C over 7 hours, and the reaction is carried out while removing distilled phenol. React for another 10 hours at 320°C, then for 30 minutes.
Raise the temperature to 340°C and react at 340°C for 5 hours. After the reaction, the mixture was cooled to below 50° C., 1000 parts of acetone was gradually added, and the slurry was filtered. The resulting polymer was washed with acetone many times and dried. In this way, 886 parts of polymer were obtained.

The yield was 92% of theory. This polymer 500
400 parts of glass fiber with a diameter of 13 μm and an average length of 600 μm (form ratio 46) (accounting for 44% by weight of the composition)
Mixed, granulated and injection molded at 390°C. There were no particular problems during granulation and molding, and molded products with good surface conditions were obtained. The tensile strength was 820 Kg/cm ² and the elongation at break was 4.3%, which were satisfactory values. The molding shrinkage rate was as small as 2/1000.

Claims (1)

[Claims] 1. General formula (In the formula, X is a hydrocarbon group having 1 to 10 carbon atoms, -
O-, -SO ₂ -, -SO-, -S-, -CO-, and m and n are 0 or 1. d≠0, and the oxybenzoic acid moiety is 50% or more.
When e, f≠0, e/f is a value from 0.90 to 1.10, and when e=f=0, the oxybenzoic acid moiety is a copolymer of at least two or more selected from ortho, meta, and para forms. It is. ), the injection moldable wholly aromatic copolyester resin has a diameter of 5 to
A wholly aromatic copolyester resin composition obtained by filling 25 to 60 weight percent of the entire composition with glass fibers having a diameter of 20 μm and an average length of 30 to 1000 μm. 2. The wholly aromatic copolyester resin composition according to claim 1, which has a morphology ratio of 3 to 100, expressed as a ratio between the length and diameter of the glass fibers. 3. The wholly aromatic copolyester resin composition according to claim 1, wherein the glass fibers are cut and/or crushed.